CN107082876A - A kind of flame retardant type polyester resin, its preparation method and the powdery paints comprising it - Google Patents
A kind of flame retardant type polyester resin, its preparation method and the powdery paints comprising it Download PDFInfo
- Publication number
- CN107082876A CN107082876A CN201710374270.2A CN201710374270A CN107082876A CN 107082876 A CN107082876 A CN 107082876A CN 201710374270 A CN201710374270 A CN 201710374270A CN 107082876 A CN107082876 A CN 107082876A
- Authority
- CN
- China
- Prior art keywords
- polyester resin
- powdery paints
- bromo
- thing
- pyromellitic acid
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 51
- 239000004645 polyester resin Substances 0.000 title claims abstract description 51
- 239000003973 paint Substances 0.000 title claims abstract description 37
- 239000003063 flame retardant Substances 0.000 title claims abstract description 14
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 trihydroxy methyl phosphorous Chemical compound 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 22
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims abstract description 19
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 claims abstract description 15
- QPBGNSFASPVGTP-UHFFFAOYSA-N 2-bromoterephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C(Br)=C1 QPBGNSFASPVGTP-UHFFFAOYSA-N 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical group OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- 238000011938 amidation process Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical group O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims 1
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 10
- 239000000835 fiber Substances 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 21
- 239000000843 powder Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 235000015511 Liquidambar orientalis Nutrition 0.000 description 6
- 241000736148 Styrax Species 0.000 description 6
- 239000004870 Styrax Substances 0.000 description 6
- 235000000126 Styrax benzoin Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000013035 low temperature curing Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LVDKZNITIUWNER-UHFFFAOYSA-N Bronopol Chemical class OCC(Br)(CO)[N+]([O-])=O LVDKZNITIUWNER-UHFFFAOYSA-N 0.000 description 1
- 241000675108 Citrus tangerina Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of flame retardant type polyester resin, its preparation method and the powdery paints comprising it.The polyester resin is made by following primary raw material through copolyreaction：The propane diols of 2 bromine, 2 nitro 1,3, neopentyl glycol, trimethylol melamine, trihydroxy methyl phosphorous oxide, four bromo terephthalic acids, Pyromellitic Acid diamides thing, end-capping reagent.The activity for the polyester resin that the present invention finally gives is higher, can be solidified at 120 DEG C, it is adaptable to which the wooden material of medium density fibre board (MDF) class, film-forming is excellent.Ignition-proof element bromine, nitrogen and phosphorus containing high level in polyester segment simultaneously, excellent flame retardancy, oxygen index (OI) can reach more than 30.
Description
Technical field
The invention belongs to technical field of coatings, and in particular to a kind of flame retardant type polyester resin, its preparation method and include it
Powdery paints.
Background technology
Polyester resin is the raw material for manufacturing polyester fiber, coating, film and engineering plastics, generally by binary acid and binary
Alcohol is made through esterification and polycondensation reaction.A common feature on this kind of polymer architecture be each chain internode of its macromolecular all
It is to be connected with ester group, therefore is commonly referred to as polyester.Polyester has that bright, plentiful, hardness is high, physical and mechanical properties is good and chemically-resistant is rotten
The advantages of corrosion, adhesive force, impact resistance and preferable wearability.With the development of science and technology, increasing saturated polyester tree
Fat prod is applied to high performance field.
Wherein application of the polyester resin in coating industry is extremely wide.And powdery paints is especially more related to and used
Polyester resin.Powdery paints is a kind of new to be free of the solid powdery coating of solvent 100%.Powdery paints is and general coating
Entirely different form, it is present with the state of attritive powder.Due to without using solvent, so referred to as powdery paints.Powder
Last coating has solvent-free, pollution-free, recyclable, environmentally friendly, the saving energy and resource, reduced labor intensity and coating machinery intensity
High the features such as.
Traditional powdery paints is basic without fire resistance, and very big peace is had if it is used on medium density fibre board (MDF)
Full hidden danger.Because medium density fibre board (MDF) is greatly used for interior with transparent powder paint, wood grain itself dress attractive in appearance is being kept
While decorations property, because without filler and pigment, ground is timber again, therefore, there is larger potential safety hazard in easy firing.
The content of the invention
Therefore, an object of the present invention is to provide a kind of flame retardant type polyester resin, the polyester segment of the polyester resin
In ignition-proof element bromine, nitrogen and phosphorus containing high level, excellent flame retardancy, oxygen index (OI) can reach more than 30.
For up to above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of flame retardant type polyester resin, is made by following primary raw material through copolyreaction：The bromo- 2- nitros -1,3- of 2- the third two
Alcohol, neopentyl glycol, trimethylol melamine, trihydroxy methyl phosphorous oxide, four bromo terephthalic acids, Pyromellitic Acid diamides
Thing, end-capping reagent.
Present invention use bromine containing ignition-proof element, nitrogen and the bromo- 2- nitros -1,3- propane diols of the higher monomer of P elements such as 2-,
Trimethylol melamine, trihydroxy methyl phosphorous oxide, four bromo terephthalic acids, Pyromellitic Acid diamides thing are used as segment master
Body, cooperates and make it that the ignition-proof element content of gained polyester is higher, excellent flame retardancy, oxygen index (OI) reaches more than 30, can
The field higher for flame-retardancy requirements such as medium density fibre board (MDF)s.
Preferably, the Pyromellitic Acid diamides thing by pyromellitic acid anhydride and tribromaniline in organic solvent
Amidation process is carried out to obtain.
Preferably, the mol ratio of pyromellitic acid anhydride and tribromaniline is 1:1-4, for example, 1:1.2、1:1.5、1:
1.8、1:2.3、1:3、1:3.4、1:3.8 etc., preferably 1:2.
Preferably, the organic solvent is N, N-dimethylformamide.
Preferably, the temperature of amidation process be 110-150 DEG C, for example, 114 DEG C, 118 DEG C, 123 DEG C, 128 DEG C, 133
DEG C, 137 DEG C, 142 DEG C, 146 DEG C, 149 DEG C etc., preferably 130 DEG C, the time is more than 2h, for example, 2.5h, 3.2h, 4h, 4.5h
Deng preferably 4h.
Preferably, organic solvent removing is obtained into the higher Pyromellitic Acid diamides thing of bromine content after reaction terminates.
Preferably, the end-capping reagent is trimellitic anhydride.
Preferably, polyester resin of the present invention is made by following primary raw material through copolyreaction：The bromo- 2- nitre of 2-
Base -1,3-PD 20-30mol%, for example, 22mol%, 24mol%, 26mol%, 28mol% etc., neopentyl glycol 5-
15mol%, for example, 7mol%, 9mol%, 11mol%, 14mol% etc., trimethylol melamine 5-10mol%, for example
For 7mol%, 9mol% etc., for example, trihydroxy methyl phosphorous oxide 2-5mol%, 3.5mol%, 4.6mol% etc., Pyromellitic Acid
Diamides thing 20-35mol%, for example, 22mol%, 24mol%, 26mol%, 28mol%, 33mol% etc., tetrabromo is to benzene two
Formic acid 10-25mol%, for example, 12mol%, 15mol%, 19mol%, 22mol%, 24mol% etc., trimellitic anhydride 5-
10mol%, for example, 7mol%, 9mol% etc., the molar percentage of each above-mentioned raw material is that each feed molar number accounts for above-mentioned original
The ratio of the total mole number of material, the catalyst amount that copolyreaction is used is the 0.1-0.3% of raw material gross mass, is, for example,
0.11%th, 0.15%, 0.18%, 0.22%, 0.28% etc..
Preferably, used catalyst is phosphotungstic acid.
Preferably, the acid number of the polyester resin be 40-60mgKOH/g, for example, 43mgKOH/g, 48mgKOH/g,
54mgKOH/g, 58mgKOH/g etc., preferably 50-55mgKOH/g.
Preferably, the glass transition temperature (Tg) of the polyester resin be 40-55 DEG C, for example, 44 DEG C, 48 DEG C, 51 DEG C,
54 DEG C etc., preferably 45-50 DEG C.
Preferably, 90-110 DEG C of the softening point of the polyester resin, for example, 94 DEG C, 98 DEG C, 101 DEG C, 104 DEG C, 108
DEG C etc., preferably 95-105 DEG C.
The second object of the present invention is to provide a kind of preparation method of flame retardant type polyester resin of the present invention, including
Following steps：
(1) by the bromo- 2- nitros -1,3- propane diols of 2-, trimethylol melamine, neopentyl glycol, trihydroxy methyl phosphorous oxide
Melting is heated after mixing；
(2) Pyromellitic Acid diamides thing, four bromo terephthalic acids are added into mixed material obtained by step (1), simultaneously
Add catalyst, temperature reaction；
(3) formation for facilitating polyester resin under antioxidant, vacuum is added, treats that acid number is reduced to below 8-12mgKOH/g
When stop vacuumize；
(4) cool, add slow heating after end-capping reagent and produce the polyester resin to carry out acidification reaction to polyester resin.
Obtained product appearance is colourless or light yellow clear material, and acid number is 40-60mgKOH/g, and glass transition temperature (Tg) is 40-55
DEG C, softening point is 90-110 DEG C.
Preferably, the temperature of heating melting is less than 140 DEG C in step (1).
Preferably, the heating added in step (2) after catalyst is carried out under nitrogen protection.
Preferably, 220-245 DEG C, preferably 240 DEG C are warming up to.
Preferably, reaction is extremely steamed without obvious distillate.
Preferably, untill the acid number of reactant is less than 25mgKOH/g.
Preferably, temperature is no more than 245 DEG C in course of reaction.
Preferably, antioxidant is antioxidant 1076 in step (3).
Preferably, the vacuum of vacuum is 50mmHg, and the retention time is 1-3h.
The amount for wherein adding antioxidant determines suitable value, preferably total thing according to specific reaction materials and reaction condition
Expect the 0.1-0.5% of molal quantity, preferably 0.3%.
Preferably, adding end-capping reagent when being cooled to 200 ± 5 DEG C in step (4).
Preferably, 220 DEG C ± 5 are to slowly warm up to, 2-4h, preferably 3h is reacted.
Preferably, stop high temperature discharging, cooling while hot after reaction, granulate.
Preferably, cooling is carried out using the steel band with condensed water.
The third object of the present invention is to provide a kind of powdery paints, includes polyester resin of the present invention.
Other auxiliary agents commonly used in the art can also be added in the powdery paints of the present invention.Preferably, institute of the present invention
The powdery paints stated also includes a kind or 2 kinds in curing agent, curing accelerator, levelling agent, texture agent, degasser, antioxidant
Combination above.
Preferably, powdery paints of the present invention includes following raw material by weight：
Levelling agent is a kind of conventional coating additive, it can promote coating formed during drying and forming-film one it is smooth,
Smooth, uniform film.Levelling agent species is a lot, and the levelling agent species used in different coating is also not quite similar.
After coating application, have one flowing and drying and forming-film process, then gradually form one it is smooth, smooth, uniform
Film.Can film reach the characteristic of flat smooth, referred to as levelability.Shrinkage cavity be coating in levelling with being produced in film forming procedure
One of characteristic defective.During practice of construction, because levelability is bad, occur brush mark during brushing, roller marks, spray are produced during roller coating
Occur tangerine peel during painting, occur together in the drying process the phenomenons such as shrinkage cavity, pin hole, sagging, referred to as levelability it is bad, these
The generation of phenomenon reduces the decoration and defencive function of coating.
Influence the factor of coating levelability a lot, the volatilization gradient and solubility property of solvent, the surface tension of coating, wet film
Thickness and surface tension gradient, the rheological characteristic of coating, construction technology and environment etc., most important of which factor are the surfaces of coating
Wet film is produced in tension force, film forming procedure surface tension gradient and the surface tension homogenization ability on wet film top layer.Improve coating
Levelability need to consider adjustment formula and add suitable auxiliary agent, make coating that there is suitable surface tension and reduction surface
The ability of power gradient.
Levelling agent of the present invention is preferably H88 levelling agents, and the consumption of levelling agent can be according to those skilled in the art
General knowledge be added.
Styrax is called pin hole remover, is to eliminate the bubble in melted powder coating, that is to say that elimination forms film pin
The principal element of hole defect, with the use of that can make to be made, film is more smooth, smooth, uniform, densification with levelling agent for it.As excellent
The mass ratio of choosing, styrax and levelling agent is 1:1-5, preferably 1:2.
Preferably, powdery paints of the present invention includes following raw material by weight：
The powdery paints of the present invention can be prepared using method as known in the art, for example with comprising the following steps
Method：：By dosage than heterogeneity be put into high-speed mixer and be sufficiently mixed uniform, then feed the mixture into screw rod and squeeze
Go out in machine and fully melt and knead, then extrusion, tabletting, crushing, obtain described flame retardant type powdery paints.
The activity for the polyester resin that the present invention to finally give by unique raw material and proportioning is higher, can be 120
DEG C solidified, it is adaptable to which the wood quality such as medium density fibre board (MDF), film-forming is excellent.Contain simultaneously in polyester segment containing higher
Ignition-proof element bromine, nitrogen and the phosphorus of amount, excellent flame retardancy, oxygen index (OI) can reach more than 30.Polyester tree provided by the present invention
Coating made from fat has excellent fire resistance.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
A kind of flame retardant type polyester resin, its raw material composition and mol ratio are：The bromo- 2- nitros -1,3- propane diols of 2-
4.8mol, neopentyl glycol 1.5mol, trimethylol melamine 1.2mol, trihydroxy methyl phosphorous oxide 0.5mol, Pyromellitic Acid
Diamides thing 5.0mol, four bromo terephthalic acid 2.5mol, trimellitic anhydride 1.2mol, antioxidant 10760.05mol.
The preparation method of above-mentioned polyester resin comprises the following steps：
A, by the bromo- 2- nitros -1,3- propane diols of the 2- of formula ratio, trimethylol melamine, neopentyl glycol, trihydroxy methyl
Phosphorous oxide is added in blender, and the heating melting below 140 DEG C；
B, the Pyromellitic Acid diamides thing of addition formula ratio, four bromo terephthalic acids into above-mentioned polyols blend, together
When add material gross mass 0.1-0.2% phosphotungstic acid as catalyst, under nitrogen protection progressively temperature reaction to without bright
Aobvious distillate is steamed, and reactant acid number be less than 25mgKOH/g untill；Reaction temperature does not exceed 245 DEG C；
The appropriate antioxidant 1076 of C, addition, keeps 50mmHg vacuum 1-3h, facilitates the formation of polyester resin, treat
Acid number stops pulling vacuum when being reduced to 8-12mgKOH/g；
D, when being cooled to 200 DEG C, the end-capping reagent trimellitic anhydride of formula ratio is added, and be to slowly warm up to 220 DEG C to polyester
Resin carries out acidification reaction 3h, finally high temperature discharging, and cool down polyester resin with the steel band with condensed water while hot, then crushes and makes
Grain, you can obtain described flame retardant type polyester resin.
Prepared powdery paints is 52mgKOH/g with low temperature curing type polyester resin acid number, and glass transition temperature (Tg) is
45 DEG C, 98 DEG C of softening point.
Embodiment 2
It is same as Example 1, except raw material constitutes as follows：The bromo- 2- nitros -1,3- propane diols 2.0mol of 2-, neopentyl glycol
1.0mol, trimethylol melamine 1.0mol, trihydroxy methyl phosphorous oxide 0.5mol, Pyromellitic Acid diamides thing 3.5mol,
Four bromo terephthalic acid 1.0mol, trimellitic anhydride 1.0mol, antioxidant 10760.01mol.
Prepared powdery paints is 45mgKOH/g with low temperature curing type polyester resin acid number, and glass transition temperature (Tg) is
43 DEG C, 94 DEG C of softening point.
Embodiment 3
It is same as Example 1, except raw material constitutes as follows：The bromo- 2- nitros -1,3- propane diols 3.0mol of 2-, neopentyl glycol
1.5mol, trimethylol melamine 0.5mol, trihydroxy methyl phosphorous oxide 0.2mol, Pyromellitic Acid diamides thing 2.0mol,
Four bromo terephthalic acid 2.3mol, trimellitic anhydride 0.5mol, antioxidant 10760.03mol.
Prepared powdery paints is 55mgKOH/g with low temperature curing type polyester resin acid number, and glass transition temperature (Tg) is
52 DEG C, 104 DEG C of softening point.
Embodiment 4
It is same as Example 1, except raw material constitutes as follows：The bromo- 2- nitros -1,3- propane diols 2.5mol of 2-, neopentyl glycol
1.2mol, trimethylol melamine 0.8mol, trihydroxy methyl phosphorous oxide 0.4mol, Pyromellitic Acid diamides thing 2.5mol,
Four bromo terephthalic acid 2.0mol, trimellitic anhydride 0.6mol, antioxidant 10760.02mol.
Prepared powdery paints is 59mgKOH/g with low temperature curing type polyester resin acid number, and glass transition temperature (Tg) is
48 DEG C, 96 DEG C of softening point.
Comparative example 1
It is same as Example 1, except not containing 2- bromo-2-nitro-1,3-propylene glycols in raw material composition.
Comparative example 2
It is same as Example 1, except not containing trimethylol melamine in raw material composition.
Comparative example 3
It is same as Example 1, except not containing trihydroxy methyl phosphorous oxide in raw material composition.
Comparative example 4
It is same as Example 1, except not containing Pyromellitic Acid diamides thing in raw material composition.
Comparative example 5
It is same as Example 1, except not containing four bromo terephthalic acids in raw material composition.
Transparent powder paint embodiment 1：550 parts of polyester resin made from embodiment 1,370 parts of E-12 epoxy resin, H88
6 parts of levelling agent, 3 parts of styrax.
Transparent powder paint embodiment 2：700 parts of polyester resin made from embodiment 2,465 parts of E-12 epoxy resin, H88
6 parts of levelling agent, 5 parts of styrax.
Transparent powder paint embodiment 3：400 parts of polyester resin made from embodiment 3,250 parts of E-12 epoxy resin, H88
4 parts of levelling agent, 2 parts of styrax.
Transparent powder paint embodiment 4：630 parts of polyester resin made from embodiment 4,400 parts of E-12 epoxy resin, H88
7 parts of levelling agent, 2.5 parts of styrax.
Transparent powder paint comparative example 1~5：It is identical with transparent powder paint embodiment 1, except polyester resin is respectively pair
Made from ratio 1~5.
Performance comparison
In the case where other physical properties such as mechanical performance are suitable, polyester is mixed according to formula obtained by above-described embodiment,
Extruded respectively with screw extruder, it is tabletting, broken, then sheet stock is pulverized and sieved powdery paints is made.Powdery paints is using quiet
Electric spray gun is sprayed on the medium density fibre board (MDF) base material after surface treated, is solidified through 120 DEG C/15min, is produced paint coatings.
By the model of preparation according to GB 8624-2012《Construction material and product burns grading performance》Method test, combustion
Burn grade and can reach more than B1 grades, be fire retardant section bar material；Part formulation even can reach A2Level, is fire-retardant type material, and
The sample sheet material that common polyester resin is made generally is B3Level, is type inflammable material, can reach B2Level, is burnable
Material.
The burning rank of the gained coating of transparent powder paint comparative example 1~5 is B2Level, is burnable material, mechanical performance
Relative to the difference of transparent powder paint embodiment 1~4.
Therefore, excellent, the excellent combination property of Flame Retardancy energy prepared by the present invention, the bromo- 2- nitros of component 2--
1,3- propane diols, trimethylol melamine, trihydroxy methyl phosphorous oxide, four bromo terephthalic acids, Pyromellitic Acid diamides thing
Mutually collaboration, interaction is indispensable.
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
1. a kind of flame retardant type polyester resin, it is characterised in that be made by following primary raw material through copolyreaction：The bromo- 2- nitros of 2--
1,3-PD, neopentyl glycol, trimethylol melamine, trihydroxy methyl phosphorous oxide, four bromo terephthalic acids, Pyromellitic Acid
Diamides thing, end-capping reagent.
2. polyester resin according to claim 1, it is characterised in that the Pyromellitic Acid diamides thing is by equal benzene tetramethyl
Acid dianhydride carries out amidation process with tribromaniline and obtained in organic solvent；
Preferably, the mol ratio of pyromellitic acid anhydride and tribromaniline is 1:1-4；
Preferably, the organic solvent is N, N-dimethylformamide；
Preferably, the temperature of amidation process is 110-150 DEG C, and the time is more than 2h；
Preferably, organic solvent removing is obtained into the higher Pyromellitic Acid diamides thing of bromine content after reaction terminates.
3. polyester resin according to claim 1 or 2, it is characterised in that the end-capping reagent is trimellitic anhydride；
Preferably, described polyester resin is made by following primary raw material through copolyreaction：The bromo- 2- nitros -1,3- propane diols of 2-
20-30mol%, neopentyl glycol 5-15mol%, trimethylol melamine 5-10mol%, trihydroxy methyl phosphorous oxide 2-
5mol%, Pyromellitic Acid diamides thing 20-35mol%, four bromo terephthalic acid 10-25mol%, trimellitic anhydride 5-
10mol%, the catalyst amount that copolyreaction is used is the 0.1-0.3% of raw material gross mass；
Preferably, used catalyst is phosphotungstic acid.
4. the polyester resin according to claim any one of 1-3, it is characterised in that the acid number of the polyester resin is 40-
60mgKOH/g, preferably 50-55mgKOH/g；
Preferably, the glass transition temperature of the polyester resin is 40-55 DEG C, preferably 45-50 DEG C；
Preferably, 90-110 DEG C of the softening point of the polyester resin, preferably 95-105 DEG C.
5. a kind of preparation method of the flame retardant type polyester resin described in any one of claim 1-4, comprises the following steps：
(1) the bromo- 2- nitros -1,3- propane diols of 2-, trimethylol melamine, neopentyl glycol, trihydroxy methyl phosphorous oxide are mixed
Heating melting afterwards；
(2) Pyromellitic Acid diamides thing, four bromo terephthalic acids are added into mixed material obtained by step (1), are added simultaneously
Catalyst, temperature reaction；
(3) add the formation for facilitating polyester resin under appropriate antioxidant, vacuum, treat acid number be reduced to 8-12mgKOH/g with
Stop vacuumizing when lower；
(4) cool, add slow heating after end-capping reagent and produce the polyester resin to carry out acidification reaction to polyester resin.
6. preparation method according to claim 5, it is characterised in that in step (1) temperature of heating melting for 140 DEG C with
Under；
Preferably, the heating added in step (2) after catalyst is carried out under nitrogen protection；
Preferably, it is warming up to 220-245 DEG C；
Preferably, reaction is extremely steamed without obvious distillate；
Preferably, untill the acid number of reactant is less than 25mgKOH/g；
Preferably, temperature is no more than 245 DEG C in course of reaction.
7. the preparation method according to claim 5 or 6, it is characterised in that antioxidant is antioxidant in step (3)
1076；
Preferably, the vacuum of vacuum is 50mmHg, and the retention time is 1-3h；
Preferably, adding end-capping reagent when being cooled to 200 ± 5 DEG C in step (4)；
Preferably, 220 DEG C ± 5 are to slowly warm up to, 2-4h, preferably 3h is reacted；
Preferably, stop high temperature discharging, cooling while hot after reaction, granulate；
Preferably, cooling is carried out using the steel band with condensed water.
8. a kind of powdery paints, it is characterised in that include the polyester resin described in claim any one of 1-4.
9. powdery paints according to claim 8, it is characterised in that described powdery paints is also comprising curing agent, solidification
One kind or two or more combination in accelerator, levelling agent, texture agent, degasser, antioxidant.
10. powdery paints according to claim 8 or claim 9, it is characterised in that described powdery paints is included by weight
Following raw material：
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108192089A (en) * | 2018-01-09 | 2018-06-22 | 句容宁武新材料股份有限公司 | A kind of preparation method of high functionality flame retardant polyether polyol |
| CN108504160A (en) * | 2018-04-12 | 2018-09-07 | 黄山正杰新材料有限公司 | A kind of powdery paints low temperature curing type polyester resin and preparation method thereof |
| CN108503810A (en) * | 2018-05-11 | 2018-09-07 | 黄山嘉恒科技有限公司 | A kind of indoor polyester resin for powder coating and preparation method, a kind of powdery paints |
| CN108586719A (en) * | 2018-04-12 | 2018-09-28 | 黄山正杰新材料有限公司 | A kind of powdery paints flame retardant type polyester resin and preparation method thereof |
| CN109575259A (en) * | 2018-12-07 | 2019-04-05 | 黄山学院 | A kind of HAA system flame retardant type polyester resin and the preparation method and application thereof |
| CN110615889A (en) * | 2019-09-19 | 2019-12-27 | 广州擎天材料科技有限公司 | Polyester resin for crystallography powder coating and preparation method and application thereof |
| CN112592468A (en) * | 2020-12-15 | 2021-04-02 | 吴春秋 | Preparation process of flame-retardant polyester resin and application of flame-retardant polyester resin in flame-retardant coating |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192089A (en) * | 2018-01-09 | 2018-06-22 | 句容宁武新材料股份有限公司 | A kind of preparation method of high functionality flame retardant polyether polyol |
| CN108504160A (en) * | 2018-04-12 | 2018-09-07 | 黄山正杰新材料有限公司 | A kind of powdery paints low temperature curing type polyester resin and preparation method thereof |
| CN108586719A (en) * | 2018-04-12 | 2018-09-28 | 黄山正杰新材料有限公司 | A kind of powdery paints flame retardant type polyester resin and preparation method thereof |
| CN108586719B (en) * | 2018-04-12 | 2021-01-26 | 黄山正杰新材料有限公司 | Flame-retardant polyester resin for powder coating and preparation method thereof |
| CN108503810A (en) * | 2018-05-11 | 2018-09-07 | 黄山嘉恒科技有限公司 | A kind of indoor polyester resin for powder coating and preparation method, a kind of powdery paints |
| CN108503810B (en) * | 2018-05-11 | 2020-07-10 | 黄山嘉恒科技有限公司 | Polyester resin for indoor powder coating, preparation method of polyester resin and powder coating |
| CN109575259A (en) * | 2018-12-07 | 2019-04-05 | 黄山学院 | A kind of HAA system flame retardant type polyester resin and the preparation method and application thereof |
| CN110615889A (en) * | 2019-09-19 | 2019-12-27 | 广州擎天材料科技有限公司 | Polyester resin for crystallography powder coating and preparation method and application thereof |
| CN110615889B (en) * | 2019-09-19 | 2021-06-08 | 擎天材料科技有限公司 | Polyester resin for crystallography powder coating and preparation method and application thereof |
| CN112592468A (en) * | 2020-12-15 | 2021-04-02 | 吴春秋 | Preparation process of flame-retardant polyester resin and application of flame-retardant polyester resin in flame-retardant coating |
| CN112592468B (en) * | 2020-12-15 | 2021-08-27 | 宁波顺声通讯设备有限公司 | Preparation process of flame-retardant polyester resin and application of flame-retardant polyester resin in flame-retardant coating |
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Effective date of registration: 20240926 Address after: No. 1, Changsheng Road, Circular Economy Park, Huizhou District, Mount Huangshan City, Anhui Province 245000 Patentee after: HUANGSHAN HUIZHOU SHUANGYI ENVIRONMENT ENGINEERING CO.,LTD. Country or region after: China Address before: No. 2, Huangping Road, Circular Economy Park, Mount Huangshan City, Anhui Province 245900 Patentee before: HUANGSHAN XIANGRONG NEW MATERIALS Co.,Ltd. Country or region before: China |